CN107142444A - A kind of preparation method of the medical zircaloy of β types of surface oxidation - Google Patents
A kind of preparation method of the medical zircaloy of β types of surface oxidation Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
- C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
- C23C8/10—Oxidising
- C23C8/12—Oxidising using elemental oxygen or ozone
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/02—Inorganic materials
- A61L27/04—Metals or alloys
- A61L27/047—Other specific metals or alloys not covered by A61L27/042 - A61L27/045 or A61L27/06
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/28—Materials for coating prostheses
- A61L27/30—Inorganic materials
- A61L27/306—Other specific inorganic materials not covered by A61L27/303 - A61L27/32
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C16/00—Alloys based on zirconium
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/12—Materials or treatment for tissue regeneration for dental implants or prostheses
Abstract
The invention discloses a kind of preparation method of the medical zircaloy of β types of surface oxidation, the ultrasound that β types Zirconium alloy material is successively carried out into material surface with acetone, absolute ethyl alcohol is washed, dried after washing：Air is heated to 550 750 DEG C in stove again, the β type zircaloys after drying are positioned in the stove full of hot-air, insulation 30min 90min；Air pressure is a standard atmospheric pressure in stove, and alloy surface forms layer of surface oxide layer, and the thickness of oxide layer is 8 μm 50 μm, that is, obtains the medical zircaloy of β types of surface oxidation.The features such as alloy material that the present invention is obtained has wearability and corrosion resistance, while also retaining good plasticity and relatively low modulus of elasticity, meets requirement of the clinical medicine to implantation material.
Description
Technical field
The invention belongs to medical composite material technical field, and in particular to the preparation side of the medical zircaloy of β types come to the surface
Method.
Background technology
Because titanium alloy has because proportion is small, specific strength is high, modulus of elasticity is low, corrosion-resistant and excellent bio-compatible
Property and formability, and aboundresources, have evolved into the comparatively ideal functional structure material of surgical implant in recent years.But
The shortcoming for being it is also it will be apparent that as implant material, its wearability is too poor.Titanium alloy as gear division be implanted into nail or
The material of the artificial bone of person, because the slip of implant and autologous organ is that inevitable, new sliding friction can cause again
The passivating film of titanium alloy self-assembling formation is destroyed, and material can form new corrosive wear again, in summary reason, the surface of material
It can become coarse.In addition, the abrasive particle of material can be embedded in the histocyte of human body, can so cause tissue inflammation, aggravation
The pain of people.In addition, abrasive particle easily forms three-body-abrasion between being implanted into material and being implanted body, so reparation is exacerbated again
The own loss of material.
Zirconium and titanium have similar property, and zircaloy has good intensity, toughness and corrosion resistance.Zirconium and titanium are all pair
The harmless element of the human body five poisonous creatures: scorpion, viper, centipede, house lizard, toad, wherein zirconium base biomedical alloy material have the standard biologic medical alloy such as conventional titanium alloy
Advantage, its Young's modulus can more be matched with skeleton.It is well known that can be for changing by carrying out surface treatment to material
The friction and wear behavior of kind material.Wherein surface treatment includes：Nitriding, oozes oxygen, and carburizing can form a floor height hard on matrix
The wearing layer of degree.Scientific research personnel utilizes the method for surface treatment for example：Differential arc oxidation, magnetron sputtering, Laser Processing etc., to obtain
Surface oxidation or nitration coating layer improve fretting wear and the decay resistance of matrix.In the method for this several surface treatment
In, oxidation is a kind of both economical simple and effective mode.Recently it is found that by the way that zircaloy is put into the air of heating
One layer of smooth fine and close oxide-film can be formed by carrying out autoxidation.And by this technology oxidation processes formation oxide-film not
Rely on the shape of matrix.Because body implanting material needs to be processed into more special shape, therefore the technology has good exploitation
Potentiality.
The content of the invention
It is an object of the invention to provide a kind of preparation method of the medical zircaloy of β types of surface oxidation, in Zr alloy surface
The oxide layer of a floor height hardness abrasion-proof corrosion-proof is obtained, while also keeping the springform that zircaloy and human body bone are more matched
Amount, the medical zircaloy of β types obtained by this method meets use requirement.
Technical solution of the present invention is as follows：
The purity of sponge zirconium, niobium and silicon that the present invention is used is commercially available to obtain all more than 99.0%.
A kind of preparation method of the medical zircaloy of β types of surface oxidation, comprises the following steps：
First, the preparation of the medical zircaloy of β types
(1) raw material is weighed, use purity for 99.9% zirconium, purity be 99.9% niobium and purity be 99.9% titanium be
Raw material, feed metal surface removes surface scale all by polishing；Weighed further according to the percentage by weight of each raw material components,
It is standby；Raw material components and percentage by weight are：Zirconium 75.12%-79.65%, niobium 20.35%-21.04%, surplus is titanium.
(2) raw material is mixed, and the raw material weighed up is uniformly mixed；
(3) prepared by melting：Melting is carried out using non-consumable type vacuum arc furnace ignition, vacuumized, vacuum degree control 4.0 ×
10-3~6 × 10-3Pa；It is passed through argon gas and carries out the air that gas washing removes residual；Melting, melting voltage are carried out under argon gas protection
For 220V, melting current control is in 93-117A, and smelting temperature is 2900 DEG C -3100 DEG C, keeps 120s-180s；After the completion of by electricity
The slow regulation of stream is to 0A, and the time of regulation is 40-60s, obtains alloy cast ingot；
(4) alloy cast ingots are quickly cooled down under the protection of argon gas in crucible copper to alloy cast ingot, crucible copper bottom
Portion is through-flow dynamic current, ingot casting is 5-10 second by the cool time of liquid to solid-state, continuation by alloy cast ingot bottom water flowing water
Cooled down in cold crucible copper, be cooled to room temperature, cool time is 10-15min, and melt back 5-8 times obtains β type zircaloys.
2nd, the preparation of surface oxide layer
(1) ultrasound that β types Zirconium alloy material is successively carried out into material surface with acetone, absolute ethyl alcohol is washed, and is dried after washing
It is dry：
(2) air is heated to 550-750 DEG C in stove, the β type zircaloys after step (1) is dried are positioned over full of heat
In the stove of air, 30min-90min is incubated；Air pressure is a standard atmospheric pressure, alloy surface formation layer of surface oxidation in stove
Layer, the thickness of oxide layer is 8 μm -50 μm, that is, obtains the medical zircaloy of β types of surface oxidation.
The case hardness of the medical zircaloy of β types of surface oxidation prepared by the present invention is 900-1306HV0.2, Young's modulus
For 23~30Gpa, the wherein zircaloy after surface oxidation has preferable plasticity during compression.
As the preferred of technical scheme, the frequency of above-mentioned ultrasound washing is 35-40KHZ, respectively in acetone and absolute ethyl alcohol
Middle ultrasound washing 15-20 minutes, the temperature of ultrasound washing is 30-40 DEG C.
Further preferably, the frequency of ultrasound washing is 40KHZ, 15 points of the ultrasound washing in acetone and absolute ethyl alcohol respectively
Clock, the temperature of ultrasound washing is 30 DEG C；Such cleaning way is not only clean, and can save the time, improves efficiency.
As the preferred of technical scheme, air is heated to 600 DEG C, soaking time by above-mentioned steps in (2) in stove
75min.Alloy surface oxidation is carried out at such a temperature, and oxide layer forms soon, and surface is uniform, and case hardness is strong, wear-resisting
It is corrosion-resistant.
Zirconium can aoxidize production ZrO2 in heating air, be closed because cubic zirconium dioxide (t-ZrO2) is beneficial to enhancing zirconium
The rotproofness of gold, the effect of orthorhombic forms zirconium dioxide (m-ZrO2) is on the contrary, transformation t-ZrO2 between wherein m-ZrO2
Belong to martensitic traoformation.M-ZrO2 and t-ZrO2 phase transformation are not only related to phase transition temperature, also and material surface compression phase
Become.Larger compression is conducive to t-ZrO2 formation, while during oxidation, with ZrO2 layers of thickness increase, material
The bearing stress of material can be released, and this can cause t-ZrO2 to m-ZrO2, and the decay resistance of material will be reduced.By
The oxide phase of material surface increases caused by oxygen oxidation is oozed, and causes the volumetric expansion of material surface, material surface by
Larger stress.Rupture and rat is occurred by larger stress, the oxide layer of surface otherwise smooth in material surface.
Because the hardness of oxide layer is higher, and can by control oxidizing temperature and oxidization time obtain one layer of fine and close oxide layer from
And the content for improving t-ZrO2 has a very big significance for lifting the wearability corrosion resistance of the medical zircaloy of β types.
Advantages of the present invention：
1. the inventive method is compared to other surfaces processing method, with spies such as method is simple, cost is low, easy realizations
Point, and it is complex-shaped due to human skeleton tooth, and as implant, the oxide layer formed by this method is independent of base
The shape of body, meets the actual condition of biomedical alloy.
2. the present invention is by β type Zr alloy surface thermal oxidations, in alloy surface formation layer of oxide layer, the oxidation
Layer fast growth, dense structure and surface are smooth, and the performance with wear resistant corrosion resistant, case hardness reaches 900-1306HV,
So that the overall performance of alloy is strengthened.
3. the inventive method not only obtains the oxide layer of quality wear resistant corrosion resistant, while also still remain good plasticity
The modulus of elasticity (23~30GPa) matched with skeleton, meets clinical medicine domain, implantation material is needed good
Wearability, corrosion resistance, the requirement of preferable intensity and low modulus of elasticity.
Brief description of the drawings
Fig. 1 is the sample surfaces XRD material phase analysis curve maps that β types zircaloy passes through before and after thermal oxidation；(a) it is β types
Zircaloy (b) is the medical zircaloy of β types of surface oxidation.
Fig. 2 is the shape appearance figure of the medical zircaloy of β types of surface oxidation；(a).Oxidized Zr-20Nb,(b)
.Oxidized Zr-20Nb-3Ti,(c).Oxidized Zr-20Nb-7Ti。
Fig. 3 is the end face shape figure of the medical zircaloy oxide layer of β types of surface oxidation；(a).Oxidized Zr-20Nb,
(b).Oxidized Zr-20Nb-3Ti,(c).Oxidized Zr-20Nb-7Ti。
Fig. 4 carries out the electricity after dynamic potential scanning at 37 DEG C for the medical zircaloy of β types of surface oxidation in artificial saliva
Chemical attack shape appearance figure；(a).Oxidized Zr-20Nb,(b).Oxidized Zr-20Nb-3Ti,(c).Oxidized Zr-
20Nb-7Ti。
The coefficient of friction figure that Fig. 5 passes through for the β types zircaloy in the embodiment of the present invention 1 before and after surface oxidation.
The coefficient of friction figure that Fig. 6 passes through for the β types zircaloy in the embodiment of the present invention 2 before and after surface oxidation.
Fig. 7 be the embodiment of the present invention 3 in β types zircaloy pass through surface oxidation before and after coefficient of friction figure.
Fig. 8 is the wear morphology figure of the medical zircaloy of β types of surface oxidation；(a).Oxidized Zr-20Nb,(b)
.Oxidized Zr-20Nb-3Ti,(c).Oxidized Zr-20Nb-7Ti。
Fig. 9 is the wear weight loss figure of the medical zircaloy of β types of surface oxidation.
Figure 10 is the compression stress strain curve figure that β types zircaloy passes through before and after surface oxidation treatment.
Specific embodiment
With reference to instantiation, the present invention is described further, but protection scope of the present invention does not limit to reality
Apply the scope that example is represented.
Embodiment 1
The medical zirconium alloy of β types of surface oxidation is standby, obtains by the following method：
1. the preparation of β type zircaloys
(1) raw material prepares：The composition and percentage of raw material：The mass fraction of zirconium is 79.65%, and the mass fraction of niobium is
20.35%.(zirconium and 20% niobium that material correspondence molar fraction is 80%, i.e., labeled as Zr-20Nb) material purity is
99.9%, all it is block sample, grain size is controlled below 2 centimetres.Before samples weighing is carried out, all specimen surfaces are all
By polishing, surface scale is removed.
(2) raw material is mixed, and the raw material weighed up is uniformly mixed；
(3) prepared by melting：Melting is carried out using non-consumable type vacuum arc furnace ignition, first vacuumized, vacuum degree control 4.0 ×
10-3~6 × 10-3Pa；It is passed through argon gas and carries out the air that gas washing removes residual, and carry out vacuumizing degasification on this basis, very
Reciprocal of duty cycle is controlled 4.0 × 10-3~6 × 10-3Pa, is finally passed through argon gas again, and air pressure is an atmospheric pressure, and melting voltage is
220V, melting current control is in 93A, and smelting temperature is 2900 DEG C, keeps 180s.Then electric current is slowly adjusted to 0A again, adjusted
The time of section is 40-60s, obtains alloy cast ingot.
(4) alloy cast ingot is quickly cooled down under the protection of inert argon in crucible copper to ingot casting, crucible copper bottom
Through-flow dynamic current.Ingot casting by liquid to solid-state cool time be 5-10 second, continuation by alloy bottom water flowing cold-crucible
Cooled down in copper, be cooled to room temperature, cool time is 10min, and melt back 8 times obtains β type zircaloys.
2. the preparation of surface oxide layer
(5) pretreatment of surface oxidation sample：β type zircaloys are cut into by block sample using WEDM,
And grinding process is carried out to β types Zr alloy surface, ultrasonic washing, washing are successively carried out to zircaloy using acetone and absolute ethyl alcohol
After dry, wherein ultrasound washing frequency be 40KHZ, respectively in acetone and absolute ethyl alcohol ultrasound washing 15 minutes, ultrasonic water
The temperature washed is 30 DEG C.
(6) surface oxidation treatment：Air is heated to 700 DEG C in stove, the β type zircaloys dried are positioned over and are full of
In the stove of hot-air, the air pressure in stove is a standard atmospheric pressure.From sample be put into stove in begin to timing, soaking time is
60min；Afterwards can be in Zr alloy surface formation layer of surface oxide layer, the thickness of oxide layer is 43.5 μm, that is, obtains Surface Oxygen
The medical zircaloy of β types of change.
Embodiment 2
The medical zirconium alloy of β types of surface oxidation is standby, obtains by the following method：
1. the preparation of β type zircaloys
(1) raw material prepares：The composition and percentage of raw material：The mass fraction of zirconium is 77.76%, and the mass fraction of niobium is
20.64%, the mass fraction 1.60% of titanium.(zirconium that material correspondence molar fraction is 77%, 20% niobium and 3% titanium, that is, mark
It is designated as Zr-20Nb-3Ti) material purity is 99.9%, is all block sample, and grain size is controlled below 2 centimetres.
Carry out before samples weighing, all specimen surfaces remove surface scale all by polishing.
(2) raw material is mixed, and the raw material weighed up is uniformly mixed；
(3) prepared by melting：Melting is carried out using non-consumable type vacuum arc furnace ignition, first vacuumized, vacuum degree control 4.0 ×
10-3~6 × 10-3Pa；It is passed through argon gas and carries out the air that gas washing removes residual, and carry out vacuumizing degasification on this basis, very
Reciprocal of duty cycle is controlled 4.0 × 10-3~6 × 10-3Pa, is finally passed through argon gas again, and air pressure is an atmospheric pressure, and melting voltage is
220V, melting current control is in 100A, and smelting temperature is 3000 DEG C, keeps 150s.Then electric current is slowly adjusted to 0A again, adjusted
The time of section is 40-60s, obtains alloy cast ingot.
(4) alloy cast ingot is quickly cooled down under the protection of inert argon in crucible copper to ingot casting, crucible copper bottom
Through-flow dynamic current.Ingot casting by liquid to solid-state cool time be 5-10 second, continuation by alloy bottom water flowing cold-crucible
Cooled down in copper, be cooled to room temperature, cool time is 15min, and melt back 8 times obtains β type zircaloys.
2. the preparation of surface oxide layer
(5) pretreatment of surface oxidation sample：β type zircaloys are cut into by block sample using WEDM,
And grinding process is carried out to β types Zr alloy surface, ultrasonic washing, washing are successively carried out to zircaloy using acetone and absolute ethyl alcohol
After dry, wherein ultrasound washing frequency be 40KHZ, respectively in acetone and absolute ethyl alcohol ultrasound washing 15 minutes, ultrasonic water
The temperature washed is 30 DEG C.
(6) surface oxidation treatment：Air is heated to 600 DEG C in stove, the β type zircaloys dried are positioned over and are full of
In the stove of hot-air, the air pressure in stove is a standard atmospheric pressure.From sample be put into stove in begin to timing, soaking time is
75min；Afterwards can be in Zr alloy surface formation layer of surface oxide layer, the thickness of oxide layer is 22.6 μm, that is, obtains Surface Oxygen
The medical zircaloy of β types of change.
Embodiment 3
The medical zirconium alloy of β types of surface oxidation is standby, obtains by the following method：
1. the preparation of β type zircaloys
(1) raw material prepares：The composition and percentage of raw material：The mass fraction of zirconium is 75.15%, and the mass fraction of niobium is
21.04%, the mass fraction 3.81% of titanium.(zirconium that respective material correspondence molar fraction is 73%, 20% niobium and 7% titanium,
Be labeled as Zr-20Nb-7Ti) material purity is 99.9%, is all block sample, grain size control 2 centimetres with
Under.Before samples weighing is carried out, all specimen surfaces remove surface scale all by polishing.
(2) raw material is mixed, and the raw material weighed up is uniformly mixed；
(3) prepared by melting：Melting is carried out using non-consumable type vacuum arc furnace ignition, first vacuumized, vacuum degree control 4.0 ×
10-3~6 × 10-3Pa；It is passed through argon gas and carries out the air that gas washing removes residual, and carry out vacuumizing degasification on this basis, very
Reciprocal of duty cycle is controlled 4.0 × 10-3~6 × 10-3Pa, is finally passed through argon gas again, and air pressure is an atmospheric pressure, and melting voltage is
220V, melting current control is in 117A, and smelting temperature is 3100 DEG C, keeps 120s.Then electric current is slowly adjusted to 0A again, adjusted
The time of section is 40-60s, obtains alloy cast ingot.
(4) alloy cast ingot is quickly cooled down under the protection of inert argon in crucible copper to ingot casting, crucible copper bottom
Through-flow dynamic current.Ingot casting by liquid to solid-state cool time be 5-10 second, continuation by alloy bottom water flowing cold-crucible
Cooled down in copper, be cooled to room temperature, cool time is 10min, and melt back 8 times obtains β type zircaloys.
2. the preparation of surface oxide layer
(5) pretreatment of surface oxidation sample：β type zircaloys are cut into by block sample using WEDM,
And grinding process is carried out to β types Zr alloy surface, ultrasonic washing, washing are successively carried out to zircaloy using acetone and absolute ethyl alcohol
After-blow is dried, wherein the frequency of ultrasonic washing is 40KHZ, ultrasound washing 15 minutes in acetone and absolute ethyl alcohol, ultrasonic respectively
The temperature of washing is 30 DEG C.
(6) surface oxidation treatment：Air is heated to 550 DEG C in stove, the β type zircaloys dried are positioned over and are full of
In the stove of hot-air, the air pressure in stove is a standard atmospheric pressure.From sample be put into stove in begin to timing, soaking time is
30min；Afterwards can be in Zr alloy surface formation layer of surface oxide layer, the thickness of oxide layer is 8 μm, that is, obtains surface oxidation
The medical zircaloy of β types.
Properties of product are detected：
First, material morphology observation and thing are mutually detected
The medical zircaloy of β types of the β types zircaloy obtained in the above embodiments 1-3, surface oxidation is subjected to XRD respectively
(a) is β type Zr alloy surface XRD material phase analysis curve maps to the result that thing is mutually detected as shown in Figure 1.(b) it is the β types of surface oxidation
Medical Zr alloy surface XRD material phase analysis curve maps.There is figure to understand the main phase composition of the material after the oxidation in embodiment
Composition is m-ZrO2, t-ZrO2 and 6ZrO2-Nb2O5Phase, wherein ZrO2 and 6ZrO2-Nb2O5It is nontoxic to human body.And
As biomedical alloy, good corrosion resistance is the big service index of one, and scientific research personnel has found t-ZrO2 to lifting material
Wearability it is favourable, by adjust oxidization time and its temperature we by XRD find 2 θ=~30 ° of θ of and 2=~50 °
Place is found that stronger t-ZrO2 peaks, and this, which might mean that, wherein higher t-ZrO2 contents.
Material surface and end face are observed using Optical microscope and SEM, as a result as shown in Figures 2 and 3,
The medical smooth densification in Zirconium alloy material surface of β types of the surface oxidation of the surface topography observation result display present invention, to alloy material
The result that the end face of material is observed shows that oxide layer and matrix metallurgical binding are close.
2nd, material properties test
The medical zirconium of β types zircaloy and the β types of surface oxidation obtained using HV1000 Vickers to embodiment 1-3 is closed
Golden sample carries out hardness test.As a result it is as follows：
In embodiment 1, without the hardness 225HV0.2 of the β-Zr alloys of oxidation processes, the medical zirconium of β types of surface oxidation
The hardness of the oxide layer of alloy is 1252HV0.2.
In embodiment 2, without the hardness 254HV0.2 of the β-Zr alloys of oxidation processes, the medical zirconium of β types of surface oxidation
The hardness of the oxide layer of alloy is 1306HV0.2.
In embodiment 3, without the hardness 267HV0.2 of the β-Zr alloys of oxidation processes, the medical zirconium of β types of surface oxidation
The hardness of the oxide layer of alloy is 934HV0.2.
The medical zircaloy of β types of surface oxidation is carried out using 2mv/s speed in -1.5V to+3V in artificial saliva
Electrochemical corrosion test is tested, and as a result erosion profile as shown in figure 4, show the oxide layer of alloy surface with preferably corrosion-resistant
Property, erosion profile result is shown based on spot corrosion.
Using pin disk friction wear testing machine 0.9MPa load β types zircaloy and Surface Oxygen to not oxidised processing
The medical zircaloy of β types of change carries out friction and wear behavior test, and coefficient of friction and wear morphology are as shown in Fig. 5~Fig. 8.Experiment knot
Fruit shows that, compared to β type zircaloys, the fretting wear coefficient of the medical zircaloy of β types of surface oxidation is significantly reduced.Fig. 9
The wear extent of the medical zircaloy of β types of surface oxidation after display oxidation is less than matrix an order of magnitude.
Using instro-8801 test systems to the Mechanics Performance Testing by the sample before and after surface oxidation, according to rule
Grid material is processed as 5mm × 5mm × 10mm, and result of the test is as shown in Figure 10：
Embodiment 1, without oxidation processes β-Zr alloys modulus of elasticity be 23.260GPa, bearing 40% modeling
There is not any obvious yield phenomenon in material after property.In the medical zirconium of β types of the surface oxidation obtained after surface oxidation
The modulus of elasticity of alloy is 24.960GPa, and in the deformation Jing Guo 40% plasticity, any yield phenomenon does not occur yet in material.
Embodiment 2, without oxidation processes β-Zr alloys modulus of elasticity be 28.235GPa, bearing 40% modeling
There is not any obvious yield phenomenon in material after property.In the medical zirconium of β types of the surface oxidation obtained after surface oxidation
The modulus of elasticity of alloy is 29.298GPa, and in the deformation Jing Guo 40% plasticity, any yield phenomenon does not occur yet in material.
Embodiment 3, without oxidation processes β-Zr alloys modulus of elasticity be 22.970GPa, bearing 40% modeling
There is not any obvious yield phenomenon in material after property.In the medical zirconium of β types of the surface oxidation obtained after surface oxidation
The modulus of elasticity of alloy is 22.990GPa, and in the deformation Jing Guo 40% plasticity, any yield phenomenon does not occur yet in material.
Embodiment 4
The medical zirconium alloy of β types of surface oxidation is standby, obtains by the following method：
1. the preparation of β type zircaloys
(1) raw material prepares：The composition and percentage of raw material：The mass fraction of zirconium is 76.21%, and the mass fraction of niobium is
20.78%, the mass fraction 2.75% of titanium.Material purity is 99.9%, is all block sample, and grain size is controlled 2
Below centimetre.Before samples weighing is carried out, all specimen surfaces remove surface scale all by polishing.
(2) raw material is mixed, and the raw material weighed up is uniformly mixed；
(3) prepared by melting：Melting is carried out using non-consumable type vacuum arc furnace ignition, first vacuumized, vacuum degree control 4.0 ×
10-3~6 × 10-3Pa；It is passed through argon gas and carries out the air that gas washing removes residual, and carry out vacuumizing degasification on this basis, very
Reciprocal of duty cycle is controlled 4.0 × 10-3~6 × 10-3Pa, is finally passed through argon gas again, and air pressure is an atmospheric pressure, and melting voltage is
220V, melting current control is in 110A, and smelting temperature is 3100 DEG C, keeps 130s.Then electric current is slowly adjusted to 0A again, adjusted
The time of section is 40-60s, obtains alloy cast ingot.
(4) alloy cast ingot is quickly cooled down under the protection of inert argon in crucible copper to ingot casting, crucible copper bottom
Through-flow dynamic current.Ingot casting by liquid to solid-state cool time be 5-10 second, continuation by alloy bottom water flowing cold-crucible
Cooled down in copper, be cooled to room temperature, cool time is 15min, and melt back 5 times obtains β type zircaloys.
2. the preparation of surface oxide layer
(5) pretreatment of surface oxidation sample：β type zircaloys are cut into by block sample using WEDM,
And grinding process is carried out to β types Zr alloy surface, ultrasonic washing, washing are successively carried out to zircaloy using acetone and absolute ethyl alcohol
After dry, wherein ultrasound washing frequency be 35KHZ, respectively in acetone and absolute ethyl alcohol ultrasound washing 20 minutes, ultrasonic water
The temperature washed is 40 DEG C.
(6) surface oxidation treatment：Air is heated to 750 DEG C in stove, the β type zircaloys dried are positioned over and are full of
In the stove of hot-air, the air pressure in stove is a standard atmospheric pressure.From sample be put into stove in begin to timing, soaking time is
50min；Afterwards can be in Zr alloy surface formation layer of surface oxide layer, the thickness of oxide layer is 37.5 μm, that is, obtains Surface Oxygen
The medical zircaloy of β types of change.
Embodiment 5
The medical zirconium alloy of β types of surface oxidation is standby, obtains by the following method：
1. the preparation of β type zircaloys
(1) raw material prepares：The composition and percentage of raw material：The mass fraction of zirconium is 77.45%, and the mass fraction of niobium is
20.65%, the mass fraction 1.90% of titanium.Material purity is 99.9%, is all block sample, and grain size is controlled 2
Below centimetre.Before samples weighing is carried out, all specimen surfaces remove surface scale all by polishing.
(2) raw material is mixed, and the raw material weighed up is uniformly mixed；
(3) prepared by melting：Melting is carried out using non-consumable type vacuum arc furnace ignition, first vacuumized, vacuum degree control 4.0 ×
10-3~6 × 10-3Pa；It is passed through argon gas and carries out the air that gas washing removes residual, and carry out vacuumizing degasification on this basis, very
Reciprocal of duty cycle is controlled 4.0 × 10-3~6 × 10-3Pa, is finally passed through argon gas again, and air pressure is an atmospheric pressure, and melting voltage is
220V, melting current control is in 105A, and smelting temperature is 3000 DEG C, keeps 160s.Then electric current is slowly adjusted to 0A again, adjusted
The time of section is 40-60s, obtains alloy cast ingot.
(4) alloy cast ingot is quickly cooled down under the protection of inert argon in crucible copper to ingot casting, crucible copper bottom
Through-flow dynamic current.Ingot casting by liquid to solid-state cool time be 5-10 second, continuation by alloy bottom water flowing cold-crucible
Cooled down in copper, be cooled to room temperature, cool time is 15min, and melt back 6 times obtains β type zircaloys.
2. the preparation of surface oxide layer
(5) pretreatment of surface oxidation sample：β type zircaloys are cut into by block sample using WEDM,
And grinding process is carried out to β types Zr alloy surface, ultrasonic washing, washing are successively carried out to zircaloy using acetone and absolute ethyl alcohol
After dry, wherein ultrasound washing frequency be 40KHZ, respectively in acetone and absolute ethyl alcohol ultrasound washing 15 minutes, ultrasonic water
The temperature washed is 30 DEG C.
(6) surface oxidation treatment：Air is heated to 550 DEG C in stove, the β type zircaloys dried are positioned over and are full of
In the stove of hot-air, the air pressure in stove is a standard atmospheric pressure.From sample be put into stove in begin to timing, soaking time is
90min；Afterwards can be in Zr alloy surface formation layer of surface oxide layer, the thickness of oxide layer is 32.4 μm, that is, obtains Surface Oxygen
The medical zircaloy of β types of change.
Claims (8)
1. a kind of preparation method of the medical zircaloy of β types of surface oxidation, it is characterised in that：Comprise the following steps：
(1) ultrasound that β types Zirconium alloy material is successively carried out into material surface with acetone, absolute ethyl alcohol is washed, and is dried after washing：
(2) air is heated to 550-750 DEG C in stove, the β type zircaloys after step (1) is dried are positioned over full of hot-air
Stove in, be incubated 30min-90min；Air pressure is a standard atmospheric pressure, alloy surface formation layer of surface oxide layer, oxygen in stove
The thickness for changing layer is 8 μm -50 μm, that is, obtains the medical zircaloy of β types of surface oxidation.
2. the preparation method of the medical zircaloy of β types of surface oxidation according to claim 1, it is characterised in that：The β types
Zircaloy raw material components and percentage by weight are：Zirconium 75.12%-79.65%, niobium 20.35%-21.04%, surplus is titanium.
3. the preparation method of the medical zircaloy of β types of surface oxidation according to claim 1, it is characterised in that：The table
The medical Zr alloy surface hardness of β types of face oxidation is 900-1306HV0.2, and Young's modulus is 23~30Gpa.
4. the preparation method of the medical zircaloy of β types of surface oxidation according to claim 1, it is characterised in that：Ultrasonic water
The frequency washed is 35-40KHZ, respectively ultrasound washing 15-20 minutes in acetone and absolute ethyl alcohol, and the temperature of ultrasound washing is
30-40℃。
5. the preparation method of the medical zircaloy of β types of surface oxidation according to claim 1, it is characterised in that：Ultrasonic water
The frequency washed is 40KHZ, respectively ultrasound washing 15 minutes in acetone and absolute ethyl alcohol, and the temperature of ultrasound washing is 30 DEG C.
6. the preparation method of the medical zircaloy of β types of surface oxidation according to claim 1, it is characterised in that：The step
Air is heated to 600 DEG C, soaking time 75min in (2) in stove suddenly.
7. the preparation method of the medical zircaloy of β types of surface oxidation according to claim 1, it is characterised in that：The β types
The preparation process of medical zircaloy is as follows：
(1) raw material is weighed, use purity for 99.9% zirconium, purity be 99.9% niobium and purity be 99.9% titanium be former
Material, feed metal surface removes surface scale all by polishing；Weighed further according to the percentage by weight of each raw material components, it is standby
With；
(2) raw material is mixed, and the raw material weighed up is uniformly mixed；
(3) prepared by melting：Melting is carried out using non-consumable type vacuum arc furnace ignition, vacuumized, vacuum degree control is 4.0 × 10-3~6
×10-3Pa；It is passed through argon gas and carries out the air that gas washing removes residual；Melting is carried out under argon gas protection, melting voltage is 220V,
Melting current control is in 93-117A, and smelting temperature is 2900 DEG C -3100 DEG C, keeps 120s-180s；After the completion of electric current is slow
Regulation is to 0A, and the time of regulation is 40-60s, obtains alloy cast ingot；
(4) alloy cast ingot is quickly cooled down under the protection of argon gas in crucible copper to alloy cast ingot, and crucible copper bottom is through-flow
Dynamic current, ingot casting is 5-10 seconds by the cool time of liquid to solid-state, continuation by alloy cast ingot bottom water flowing cold-crucible
Cooled down in copper, be cooled to room temperature, cool time is 10-15min, and melt back obtains β type zircaloys.
8. the preparation method of the medical zircaloy of β types of the surface oxidation according to right 5, it is characterised in that：The raw material is anti-
Remelt refining number of times is 5-8 times.
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